Method and apparatus for water management of a fuel cell system

ABSTRACT

A method and apparatus for water management in a direct oxidation fuel cell system includes a direct oxidation fuel cell, including: a housing surrounding an anode, a cathode, a protonically conductive electronically non-conductive membrane electrolyte disposed between the anode and the cathode, a current collector, and a gas-permeable liquid-impermeable membrane disposed on a side of the cathode opposite the electrolyte. Excess water accumulation is removed from an area between the membrane electrolyte and the gas-permeable liquid-impermeable membrane by a pressure differential generated, preferably, by a pump. The pressure differential draws air to the surface of, into, or through the cathode diffusion layer. The pump can be driven by the electricity generated by the fuel cell.

[0001] This application is a continuation-in-part of U.S. patentapplication Ser. No. 10/090,336, filed Mar. 4, 2002, which is hereinincorporated by reference in its entirety.

[0002] This invention was made with US Government Support undercooperative agreement No. 70NANB1H3010 awarded by the National Instituteof Standards and Technology Cooperative. The U.S. Government has certainrights in the invention.

BACKGROUND OF THE INVENTION

[0003] 1. Field of the Invention

[0004] The present invention relates generally to the field of directoxidation fuel cells for producing electrical energy by electrochemicaloxidation/reduction of an organic fuel, and in particular to a directoxidation fuel cell with integrated water management.

[0005] 2. The Prior Art

[0006] Fuel cell technologies present opportunities for the commercialdevelopment of long-lasting power sources for portable power andelectronics applications. With the trend toward greater portability of awide array of consumer electronics, some fuel cell technologies offerpromising alternative power sources to meet the increased demand forportable power. Fuel cells can potentially replace or favorably competewith the various types of high density batteries presently used inconsumer electronics, such as nickel metal-hydride and lithium ionbattery systems, as well as relatively inexpensive alkaline batteries.These types of batteries are less than satisfactory power sources forsuch consumer electronics as laptop computers and cellular phones eitherdue to their low power density, short cycle life, rechargability orcost. In addition, all these types of batteries present environmentalsafety concerns and costs for proper disposal.

[0007] Fuel cell systems are electricity-generating devices that convertchemical energy into useable electrical energy via a simpleelectrochemical reaction involving a fuel reactant, such as natural gas,methanol, ethanol, or hydrogen, and an oxidizing agent, typicallyambient air or oxygen. Fuel cell systems may be divided into“reformer-based” systems, i.e., those in which the fuel is processed insome fashion before it is introduced into the cell, or “directoxidation” systems, i.e., those in which the fuel is fed directly intothe cell without internal processing. Most currently availablestationary fuel cells are reformer-based fuel cells. However, fuelprocessing requirements for such cells limits the applicability of thosecells to relatively large systems.

[0008] Referring to FIG. 1, a conventional direct oxidation fuel cell 1,wherein the fuel reactant 3 is fed directly into the fuel cell 1 withoutinternal modification or oxidation, is typically constructed of an anodediffusion layer 5, a cathode diffusion layer 7, and an electrolyte 9,such as a protonically conductive electronically non-conductive membraneelectrolyte (“PCM”), that is disposed between the anode and cathodediffusion layers. Fuel reactant is introduced into the fuel cell anodeand is presented to a catalytic layer 11 intimately in contact with theanode face of the PCM. The anode catalyst layer separates hydrogen fromthe fuel reactant into protons and electrons as a result of oxidation.Upon the completion of a circuit which electrically connects the anodeand cathode of the fuel cell, protons generated by the anodic catalyticreaction pass through the membrane electrolyte to the cathode of fuelcell. Electrons generated by anodic oxidation of fuel molecules cannotpass through the membrane electrolyte, and seek a path through the loadwhich is being powered. The electrons flow away from the anode catalyst,through the anode diffusion layer, and are collected by a currentcollector 10, pass through a load (not shown), through a currentcollector 12, through the cathode diffusion layer and to the cathodecatalyst layer 13 where the electrons combine with protons and oxygen toform water.

[0009] As long as constant supplies of fuel reactant and an oxidizingagent are available to the fuel cell, it can generate electrical energycontinuously and maintain a desired power output. Hence, fuel cells canpotentially run laptop computers and mobile phones for several daysrather than several hours, while reducing or eliminating the hazards anddisposal costs associated with high density and alkaline batteries. Afurther benefit is that a fuel cell runs cleanly producing water andcarbon dioxide as by-products of the oxidation/reduction of the fuelreactant. The challenge is to develop fuel cell technology and toengineer direct fuel cell systems to meet the form and operationrequirements of small-scale or “micro” fuel cells for portableelectronics applications.

[0010] Direct methanol fuel cell (“DMFC”) systems are often multi-cell“stacks” including a number of single fuel cells joined to form a cellstack to increase the voltage potential to meet specific electricalpower requirements. The feasibility of using DMFC systems as alternativepower sources for portable electronics applications will depend upon thereduction of the size of the overall system to meet demanding formfactors, while satisfying the necessary power requirements forelectrical power applications.

[0011] In addition, DMFC systems useful for consumer electronicsapplications will require development and design engineering that willenable methanol fuel cells to self-regulate and passively generateelectrical power under relevant operating conditions, including ambientair temperature and humidity with a minimum of active humidity ortemperature regulation. Such operating conditions may further requirethe reduction or elimination of auxiliary equipment and external movingparts typically associated with present DMFC systems, such as externalfins for heat dissipation, fans for cooling and external flow pumps forsupplying pressurized gas reactants and water for sufficient membranehumidification. In addition, the volume of peripheral mechanisms orsystems, such as pumps and reservoirs used to store and supply methanolfuel and gas separators used to remove gases from liquid fuel celleffluents, will need to be reduced or eliminated in DMFC systems forportable power and consumer electronics applications.

[0012] At present, prior art DMFC systems typically operate in two basicconfigurations, a flow-through configuration and a recirculationconfiguration, as disclosed, for example in U.S. Pat. Nos. 5,992,008,5,945,231, 5,795,496, 5,773,162, 5,599,638, 5,573,866 and 4,420,544. Theflow-through configuration directly feeds methanol as a vapor or astream of either neat methanol or an aqueous solution of methanol andwater into the anode electrode of the fuel cell. Anodic oxidationby-products, specifically carbon dioxide, as well as fuel impurities andunreacted methanol fuel solution are removed from the fuel cell to theambient environment. The flow-through configuration has thedisadvantages of wasting unused fuel, and making it difficult to manageeffluent by-products. In addition, the flow-through configurationpresents problems with respect to handling the anode effluent dischargedfrom the fuel cell. Peripheral mechanisms or systems are required withthe flow-through configuration of DMFC systems to remove and dispose ofthe anode effluent discharged from the fuel cell. Such mechanism orsystems would render flow-through DMFC systems impractical for use inportable electronics applications.

[0013] The recirculation configuration of DMFC systems, however, has theadvantages of recirculating the anode effluent back into the anodeelectrode, which conserves unused methanol fuel and contains the anodeeffluent generated by the electrochemical oxidation/reduction processes.

[0014] Prior art DMFC systems with recirculation configurations addressthe problems of handling anode effluent, conserving unused methanol fueland providing a means of managing by-products of the reaction. Suchfeatures are highly advantageous for use of DMFC systems in portablepower supplies and portable consumer electronics. However, recirculationconfigurations of prior art DMFC systems must incorporate auxiliary orexternal peripheral equipment in the recirculation loops that occupyvolume and add complexity to DMFC systems due to their use of electricalpower, thus limiting the net power output of the DMFC system.

[0015] In a DMFC, it is necessary to provide sufficient quantities offuel (a mixture of water and methanol) to the catalyzed anode face ofthe PCM, and oxygen to the catalyzed cathode face of the PCM. Failure toallow sufficient quantities of the reactants to be introduced to the PCMresults in the cessation of the reactions that generate electricity in afuel cell.

[0016] During operation, the cathode diffusion layer may becomesaturated by water that is generated on the cathode face of the PCM. Thesaturation of the diffusion layer prevents oxygen from reaching thecathode face of the PCM, and causes the fuel cell's performance to becompromised, or be halted altogether. In addition, particulate airbornecontaminants may clog the openings in the structure of the cathodediffusion layer, thus further limiting the performance of the DMFC. U.S.Pat. No. 6,326,097 to Hockaday discloses the use of a disposablediffusion mat that is integrated into the external housing of the fuelcell system and is used to manage temperature and humidity, and alsoprovides some filtering characteristics as well.

[0017] Moreover, it is desirable to supply methanol to the catalyzed PCMin an aqueous solution. By doing so, methanol crossover ( a processwhereby methanol passes through the PCM without contributing to thegeneration of electricity) is reduced and the overall utility of thecell is enhanced. It is desirable to carry a more concentrated mixtureof fuel, rather than a dilute mixture, for the purpose of minimizing thevolume of the fuel cartridge or internal reservoir, and therefore thesystem. However, to ensure that the DMFC will continue generatingelectricity, sufficient oxygen must be supplied to the cathode, andunder certain operating conditions, it may be necessary to provide amethod to facilitate the removal of cathodically generated water and anyother fluids that may be present on the cathode face of the PCM, orwithin the cathode diffusion layer of the fuel cell, including but notlimited to liquid water that may be present.

[0018] Previously disclosed methods of water removal from the cathodediffusion layer of the fuel cell rely on wicking, drying, or absorptionto transport or remove cathodically generated water, or are gravitydependent. The effectiveness of these methods varies with the ambientair temperature and humidity, or the orientation of the device and aredifficult to control or vary predictably. As such they are less thanideal for use in portable electronics which will be exposed to a widevariety of conditions during use, and which require that they remainoperational during periods of rapid change of such conditions.

[0019] There remains a need, therefore, for a direct oxidation fuel cellsystem that optimizes oxygen being provided to the cathode and preventsexcess water accumulation on the cathode face of the PCM and the cathodediffusion layer of the fuel cell. Therefore, it would be desirable toprovide a method and apparatus for preventing excess water fromsaturating the cathode diffusion layer and thereby preventing oxygenfrom reaching the cathode catalyst layer, and preferably recirculatingthe excess water to adjust the fuel concentration within the fuel cellsystem, enabling the system to carry a more concentrated fuel source.

SUMMARY OF THE INVENTION

[0020] One aspect of the present invention relates to a systemincluding: a direct oxidation fuel cell, which includes a housingsurrounding an MEA, a current collector disposed on the outside of theMEA to collect and conduct electrical current to a load, and agas-permeable liquid-impermeable membrane disposed on a cathodesideouter surface of the current collector, wherein the MEA includes ananode aspect, a cathode aspect, and a PCM disposed between the anodeaspect and the cathode aspect; a source of fuel in communication withthe anode aspect; a source of oxygen in communication with the cathodeaspect, so as to produce electricity-generating reactions, includinganodic disassociation of a fuel and water mixture to produce carbondioxide, protons and electrons and a cathodic combination of protons,electrons and oxygen to produce water; and a pump in fluid communicationwith an area between the PCM and the gas-permeable liquid-impermeablemembrane, connected to remove excess water produced at the cathodeaspect.

[0021] Another aspect of the present invention relates to a systemincluding a direct oxidation fuel cell, which includes a housingsurrounding an MEA, including an anode diffusion layer, a cathodediffusion layer, and a PCM disposed between the anode diffusion layerand the cathode diffusion layer, a catalyst layer is preferably disposedon one or both faces of the PCM in intimate contact with the PCM and thediffusion layer, a current collector disposed on the outside of the MEAto collect and conduct electrical current to a load, and a gas-permeableliquid-impermeable membrane disposed on an outer cathode-side surface ofthe current collector; a source of fuel in communication with the anodeaspect of the MEA; a source of oxygen in communication with the cathodeaspect of the MEA, so as to produce electricity-generating reactions,including anodic disassociation of a fuel and water mixture to producecarbon dioxide, protons and electrons and a cathodic combination ofprotons, electrons and oxygen to produce water; and a pump in fluidcommunication with an area between the PCM and the gas-permeableliquid-impermeable membrane, connected to remove excess liquid waterproduced at the cathode.

[0022] Another aspect of the present invention is a method for managingwater in a direct oxidation fuel cell, including: providing a directoxidation fuel cell, including: a housing surrounding an MEA, whereinthe MEA includes an anode aspect, a cathode aspect and a PCM disposedbetween the anode aspect and the cathode aspect, a current collectordisposed on the outside of the MEA to collect and conduct electricalcurrent to a load, and a gas-permeable liquid-impermeable membranedisposed on a cathode-side outer surface of the current collector;providing fuel to the anode aspect of the fuel cell; providing oxygen tothe cathode aspect of the fuel cell; and removing excess wateraccumulation from an area between the PCM and the gas-permeableliquid-impermeable membrane.

[0023] Another aspect of the present invention relates to a method formanaging water in a direct oxidation fuel cell, including: providing adirect oxidation fuel cell, including a housing surrounding an MEA,wherein the MEA includes an anode diffusion layer, a cathode diffusionlayer, and a PCM disposed between the anode diffusion layer and thecathode diffusion layer, a catalyst layer is preferably disposed on oneor both faces of the PCM in intimate contact with the PCM and thediffusion layer, a current collector disposed on the outside of the MEAto collect and conduct electrical current to a load, and a gas-permeableliquid-impermeable membrane disposed on an outer cathode-side surface ofthe current collector; providing fuel to the anode diffusion layer ofthe MEA; providing oxygen to the cathode diffusion layer of the MEA; andremoving excess water accumulation from an area between the PCM and thegas-permeable liquid-impermeable membrane.

[0024] Another aspect of the present invention relates to a methodincluding: providing a direct oxidation fuel cell, including a housingsurrounding an MEA; wherein the MEA includes an anode aspect, a cathodeaspect and a PCM disposed between the anode aspect and the cathodeaspect, a current collector disposed on the outside of the MEA tocollect and conduct electrical current to a load, and a gas-permeableliquid-impermeable membrane disposed on a cathode-side outer surface ofthe MEA; providing fuel to the anode aspect of the current collector;providing oxygen to the cathode aspect of the PCM; and drawing air tothe surface of, into or through the cathode diffusion layer, preferably,via the creation of a pressure differential.

[0025] Additional features of the invention will be set forth in thedetailed description which follows, and in part will be readily apparentto those skilled in the art from the description or recognized bypracticing the invention as described in the written description andclaims hereof, as well as appended drawings.

[0026] It is to be understood that both the foregoing generaldescription and the following detailed description are merely exemplaryof the invention, and are intended to provide an overview or frameworkto understanding the nature and character of the invention as it isclaimed.

BRIEF DESCRIPTION OF THE DRAWINGS

[0027] The accompanying drawings are included to provide a furtherunderstanding of the invention, and are incorporated in and constitute apart of this specification. The drawings illustrate one or moreembodiment(s) of the invention, and together with the description serveto explain the principles and operation of the invention. In thedrawings,

[0028]FIG. 1 is a schematic diagram of a prior art DMFC;

[0029]FIG. 2 is a cross-section view of the fuel cell system in whichthe present invention is embodied;

[0030] FIGS. 3 A-C are side plan views of various embodiments of thecathode diffusion layer;

[0031]FIG. 4 is a cross-section view of an alternate embodiment of afuel cell stack;

[0032]FIG. 5 is a cross-section view of an alternate embodiment of afuel cell stack; and

[0033]FIG. 6 is a cross-section view of an alternate embodiment of afuel cell stack.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0034] The present invention provides a method and apparatus for watermanagement for a direct oxidation fuel cell system. More particularly,cathodically generated water is preferably directed to the anode whereit can be mixed with fuel from a more concentrated fuel source in orderto provide a more dilute fuel mixture. For purposes of illustration, weherein describe an illustrative embodiment of the invention as it isemployed in connection with a direct methanol fuel cell system (“DMFCsystem”), with the fuel substance being methanol or an aqueous methanolsolution. It should be understood, however, that it is within the scopeof the present invention that the water management apparatus and methodcan be readily used with other fuels that are compatible with directoxidation fuel cell systems. Thus, as used herein, the terms “fuel”,“fuel reactant”, and “fuel mixture” shall include methanol, ethanol, orcombinations thereof and aqueous solutions thereof and othercarbonaceous fuels that are suitable for use in a direct oxidation fuelcell system.

[0035]FIG. 2 shows a direct methanol fuel cell system 15 incorporatingthe water management apparatus of the present invention. The system ispreferably disposed within a casing (not shown) for use in portableapplications. In a preferred embodiment, the direct oxidation fuel cellsystem 15 contains a direct methanol fuel cell 17. The fuel cell hasanode chamber 19 and cathode chamber 21 surrounded by a housing 23. Theanode chamber and cathode chamber are separated by the PCM 25 which ispreferably coated with an anode catalyst 27 and a cathode catalyst 28. Afuel, such as methanol, is supplied to the anode chamber of the DMFCfrom a fuel source through a pump (not shown), or by using a pressurizedcartridge or other fuel delivery system depending on the particularapplication.

[0036] As will be understood by those skilled in the art, an aqueoussolution of the carbonaceous fuel (typically aqueous methanol) ispresented to a PCM typically through an anode diffusion layer 29, asshown in FIG. 2. The fuel is disassociated by the catalysts in intimatecontact with the anode face of the PCM, or which are otherwise presentin the anode and cathode chambers, which enable direct oxidation of thecarbonaceous fuel on the anode and the reduction of the products of thecathodic reaction on the cathode face of the PCM. Upon the completion ofa circuit, the protons pass through the membrane electrolyte which isimpermeable to the electrons. The electrons seek a different path tore-unite with the protons and travel through a load and thus provide theelectrical power of the cell. This separates the hydrogen protons andelectrons from the fuel molecules. The electrochemical reactionequations are as follows:

Anode: CH₃OH+H₂O=CO₂+6H⁺+6e⁻  Equation 1

Cathode: 4H⁺+4e⁻+O₂=2H₂O   Equation 2

Net Process: CH₃OH+3/2 O₂=CO₂+2H₂O   Equation 3

[0037] The anodic reaction of the direct oxidation fuel cell, asdescribed in Equation 1, produces carbon dioxide (CO₂). A gas separatorreceives the anode effluent and separates gaseous carbon dioxide fromany un-reacted methanol or aqueous methanol solution which may be sentto a pump to be reintroduced to the anode chamber as desired in aparticular application. Water is produced in the cathode chamber, by thecathodic reaction described in Equation 2. A second gas separatorreceives the cathode effluent and separates the cathodic effluent fromthe cathode into liquid (i.e., water, which may be supplied to a pump)and vapor and air, which may be released into the environment.

[0038] Direct methanol fuel cells, such as the fuel systems disclosed inU.S. Pat. Nos. 5,992,008, 5,945,231, 5,773,162, 5,599,638, 5,573,866 and4,420,544, which are herein incorporated by reference in their entirety,typically employ proton conducting, cation-exchange polymer membranesconstructed of a perfluorocarbon sulfonic acid (PFSA) ionomer, such asNAFION® commercially available from E. I. duPont de Nemours and Co.Commercially available NAFION® membranes that act as membraneelectrolytes for DMFC systems generally have a thickness of 25 to 175μm. Composite membranes are also commercially available and can act asmembrane electrolytes. Composite membranes are significantly thinnerthan homogeneous ionomeric membranes and generally have a thickness of10 to 25 μm. Such composite membranes include, for instance, apolytetrafluorotheylene (PTFE) micromesh material with PFSA-filled poresavailable from W. L. Gore, Inc. of Newark, Del.

[0039] Preferably, a catalyst layer is in intimate contact with eachface of the PCM. The catalytic layers are composed of electrocatalyststhat catalyze the electrochemical oxidation and reduction of the fuelreactant, wherein an anode electrocatalyst disassociates hydrogenprotons from the fuel reactant and a cathode electrocatalyst effectsreduction of hydrogen ions with oxygen to form water. High surface areaparticles, such as platinum and ruthenium alloy particles, are commonlyused as anode electrocatalysts, as disclosed in U.S. Pat. No. 5,523,177,which is herein incorporated by reference in its entirety. However,ternary or quaternary catalyst layers are also possible. A suitablecathode electrocatalyst is platinum-black (Pt-black) which is typicallyapplied to the membrane electrolyte to form an appropriate site forelectrochemical reduction. As used herein, the term “catalyst layer” maybe used interchangeably with the term “catalyst.” The catalyst layer issometimes referred to as being a part of the PCM, for example, whereinterfaces between the components of the fuel cell are described.

[0040] Preferably, each electrocatalyst layer is in intimate contactwith a diffusion layer. The diffusion layer allows the introduction ofreactants and removal of by-products of the electrochemical reactionsthat occur on the catalyzed surface of the PCM, and are generallyfabricated from un-catalyzed porous carbon paper or carbon cloth with alayer containing PTFE and high surface area particles. The anodediffusion layer serves to uniformly distribute the fuel mixture to thecatalyzed anode face of the PCM, while providing a path by which carbondioxide may be released. The cathode diffusion layer serves to uniformlydistribute the oxidant or air to the catalyzed cathode face of the PCM,while providing a path by which anodically generated water may beremoved from the cathode face of the membrane. The cathode diffusionlayer provides an effective supply of oxidizing agent, air or oxygen,while removing water or water vapor from the membrane electrolyte formedfrom electrochemical reduction of hydrogen ions. In addition toproviding the introduction of reactants to and removal of the productsof the energy producing reaction from the catalyzed faces of the PCM,each diffusion layer conducts electricity generated by the energyproducing reactions.

[0041] The diffusion layer is typically constructed of a porous carbonfiber paper and/or carbon cloth that is well known in the art including,although not limited to, TORAY® paper or E-TEK® cloth available fromE-Tek, Inc., Division of DeNora N. A., Inc. of Sommerset, N.J. Althoughdependent upon the material of construction, the anode diffusion layerhas a thickness generally in the range of about 150 μm to about 400 μm.The diffusion layer may be additionally treated with additives wellknown in the art, which effectively increase diffusion or otherproperties of the diffusion layer, such as, although not limited to,TEFLON® for wet-proofing, and high surface area carbon particles toenhance electrical conductivity.

[0042] The membrane electrode assembly (“MEA”) preferably includes ananode diffusion layer, a cathode diffusion layer, and a PCM disposedbetween the anode diffusion layer and the cathode diffusion layer. Acatalyst layer is preferably disposed on one or both faces of the PCM inintimate contact with the respective diffusion layer. Those skilled inthe art will recognize that preferably, the PCM, catalyst layers, anddiffusion layers are typically placed in intimate contact with, orotherwise bonded with each other and/or bonded to each other to form theMEA.

[0043] Although the specific construction of the MEA in terms ofcomponents and structure may vary, the MEA is defined as a structurewhich facilitates the introduction of reactants, the maintenance of theelectrochemical reactions and the removal of unreacted reactants andreaction products and by-products to provide an electricity generatingfuel cell. As used herein the terms “cathode”, “cathode chamber”0 and“cathode aspect of the MEA” are interchangeable and meant to designatethat portion of the fuel cell where the protons, electrons and oxygenare combined to form cathodically generated water. As used herein theterms “anode”, “anode chamber” and “anode aspect of the MEA” areinterchangeable and meant to designate that portion of the fuel cellwhere the protons, electrons and carbon dioxide are produced from theanodic disassociation of a fuel and water mixture.

[0044] Current collector plates 31 and 33 or other current collectingcomponents may be located on outer sides of the MEA of the fuel cellunit to conduct and collect electrons generated by the electrochemicaloxidation of methanol. Suitable collector plates are typicallyconstructed of carbon composites or metals, such as stainless steel andtitanium, exhibit high electronic conductivity, and do not corrode orotherwise deteriorate in the presence of methanol, water, oxygen orother reactants or by-products. Collector plates may be configured asbipolar plates and may be shaped to form flow fields having a range offlow channel geometry that provides effective mass transport ofreactants, as well as effective removal of byproducts of the reaction,including carbon dioxide and water. Alternatively, the current collectormay be a thin screen or foil that is in contact with the diffusion layerof the MEA.

[0045] In one embodiment of the present invention, the system includes:a direct oxidation fuel cell having a housing surrounding an MEA, acollector in communication with the MEA for capturing and conductingcurrent, and a gas-permeable liquid-impermeable membrane 35 disposed onan outer cathode-side surface of the current collector; a source of fueland a fuel delivery system that delivers fuel to the anode aspect of theMEA; a source of oxygen, preferably ambient air, in communication withthe cathode aspect of the MEA, so as to allow the electricity producingreactions to occur; and an apparatus for creating a pressuredifferential, such as for example, a small commercially available pump37, in fluid communication with an area between the PCM and thegas-permeable liquid-impermeable membrane, connected to remove excessliquid water produced at the cathode side of the MEA. Preferably thegas-permeable liquid-impermeable membrane is disposed on the outersurface of the cathode collector. The housing need not entirely, or evensubstantially surround the MEA, and a portion of the housing may bepartially open in order to allow the flow of oxygen and fuel.

[0046] The present invention also includes a method for managing waterin a direct oxidation fuel cell, including: providing a direct oxidationfuel cell, including a housing surrounding an MEA, a collector incommunication with the MEA for capturing and conducting current, and agas-permeable liquid-impermeable membrane disposed on an outercathode-side surface of the current collector; providing fuel to theanode aspect of the MEA; providing oxygen to the cathode aspect of theMEA; and removing excess liquid water accumulation from an area betweenthe PCM and the gas-permeable liquid-impermeable membrane.

[0047] In a preferred embodiment, a cathode diffusion layer fabricatedfrom typical materials is placed in intimate contact with the PCM, atleast one face of which has a catalyst applied to it, using methods wellknown to those skilled in the art. To the collector disposed on thecathode diffusion layer, a gas-permeable liquid barrier, preferably amembrane such as expanded PTFE, is attached to the face opposite thePCM. (FIG. 2) Alternatively, the barrier could be formed by applying aliquid to the surface of the cathode collector of the MEA, which, whendry, would form a barrier to liquids but not gasses.

[0048] The gas-permeable liquid-impermeable membrane prevents liquidwater from escaping from the cathode aspect of the MEA, preferably thecathode diffusion layer, and acts as a filter to remove particulatecontaminants from the air while at the same time creating a finitevolume against which a pressure differential is created, for example, bya pump or other apparatus capable of creating suction. For convenience,an embodiment of the present invention illustrates the use of a pump forcreating a pressure differential. However, the invention is not solimited and any apparatus capable of creating a pressure differentialsufficient to remove cathodically generated liquid water is suitable foruse in the present invention. Moreover, this pressure differentialenables a uniform removal of water from, for example, the cathodediffusion layer, allowing increased air access to the cathode aspect ofthe MEA. The invention further enables the increased introduction of airto the surface of, or the induction of air into or through the cathodeaspect of the MEA, preferably the diffusion layer. The pressuredifferential may be applied to the cathode side between thegas-permeable liquid-impermeable membrane, which is applied to thecathode-side outer surface of the MEA collector, and the PCM, so thatcathodically generated water may be removed from the cathode aspect ofthe MEA, e.g., diffusion layer, to prevent water accumulation and enablesufficient amounts of oxygen to reach the cathode face of the PCM.

[0049] As shown in FIG. 2, the pump 37 is connected to the fuel cell bya first conduit 39. One end of the first conduit 39 is connected to anopening in the cathode side of the MEA, which is in communication withthe area between the gas-permeable liquid-impermeable membrane and thePCM. The MEA may contain a channel or a plurality of channels within,for example, the cathode diffusion layer 40, for the removal of water,which can be connected to the first conduit. The other end of the firstconduit is connected to the inlet of the pump 37. A second conduit 41 isconnected to the outlet of the pump and a collection reservoir 43, asshown in FIG. 2. The second conduit 41 may be fabricated from agas-permeable liquid-impermeable material to remove any residual gassesfrom the water. In addition, a check valve 42 may be placed between thepump and the collection reservoir in order to prevent the backflow ofwater into the cathode aspect of the MEA. The collection reservoir ispreferably connected to the fuel source, wherein the pump effluent isrecirculated to adjust the fuel concentration. Alternately, the secondconduit may be connected to vent the excess water to the outsideenvironment. Power can be supplied to the pump through electrical leads(not shown) from an outside source or from the electricity produced bythe fuel cell.

[0050] The pump may apply suction at one point 45 on or within thecathode diffusion layer, as shown in FIG. 3A. However, when thediffusion layer is sufficiently large, or a smaller pump is desired, itmay be beneficial to: 1) collect water from multiple points 47 on orwithin the diffusion layer (FIG. 3B); 2) form a series of conduits orchannels 49 where fluids may flow preferentially that extends throughoutthe diffusion layer (FIG. 3C); or 3) establish a conduit with multiplecollection points perforated into the wall of the tube (not shown). Eachof these configurations facilitates a uniform collection of water and auniform introduction of air allowing improved transport of liquids andoxygen to the cathode diffusion layer leading to enhanced performance ofthe diffusion layer, and thus of the cathode and fuel cell system aswell.

[0051] Once water is collected from the cathode, it may be returned tothe anode recirculation loop, where it can be used to adjust theconcentration of the fuel, or to the anode diffusion layer. Excess watercan be eliminated from the system using methods known to those skilledin the art. The gaseous by-products and excess reagents of theelectrochemical processes are removed from the fuel cell by one or morevents by methods known to one of ordinary skill in the art. Cathodicallygenerated water may be removed from the system and is preferablyrecirculated to the fuel source by a pump. In addition, the pump may beused to apply suction to the cathode diffusion layer in order toincrease the airflow to the cathode diffusion layer, which will improvethe performance of the fuel cell system. This has been shown to beuseful where the performance of the fuel cell system is limited by therate of the cathodic half reaction.

[0052] In a further preferred embodiment, in a fuel cell stack composedof an assembly of multiple fuel cells, including those assembled in a“stack” configuration, the gas-permeable liquid-impermeable membrane canbe placed on more than one cell in a manner which provides air access tomultiple cells of the assembly. Water collection is provided at thecorner locations 51 of each gas-permeable liquid-impermeable membrane 35(FIG. 4), and/or the anode chamber. This embodiment utilizes multiplewater outlet channels, and provides a measure of orientationindependence with respect to the removal of cathodically generatedwater. The functionality of this embodiment is suited to situationswhere gravity causes the water to drain to the proper comers. Becausethere are water collection points located on different parts of thesystem, this configuration is particularly useful in situations wherethe fuel cell system will not remain in a constant orientation duringuse.

[0053] In a further preferred embodiment, wherein a fuel cell stack iscomposed of multiple cells the gas-permeable liquid-impermeable membranecan be placed on the face of each individual cathode. Water collectionis possible at single or multiple points 53 on each cell. Electricalconductivity from cell to cell could be achieved by either selectivelyconnecting cells by piercing the gas-permeable liquid-impermeablemembrane 35 or connecting around the gas-permeable liquid-impermeablemembrane 35. (FIG. 5).

[0054] In a further preferred embodiment, a fuel cell stack is composedof multiple cells 60, 60A, and 60B, wherein the gas-permeableliquid-impermeable membrane 35 is placed on the face of each individualcathode, as shown in FIG. 6. The pump 67 and fuel cell 60 are in fluidcommunication by connection to a first conduit 69. An interface 61, suchas a needle, port, or hydrophilic material, is located in-line with thefirst conduit 69 and connected to the cathode aspect of the fuel cell60. A hydrophilic element 63 may be disposed in-line with the firstconduit 69. The hydrophilic element 63 is a hydrophilic material thatdraws water away from the cathode aspect of the fuel cell. When the pump67 is off, the hydrophilic element 63 may act as a storage reservoir forexcess water, thus allowing the continuous removal of water from thecathode aspect of the fuel cell. A cathode capillary material 66 is ahydrophilic material disposed between the PCM 25 and the gas-permeableliquid-impermeable membrane 35 that absorbs water that is present on thecathode aspect of the PCM 25. In the presently preferred embodiment, thecathode capillary material 66 is in contact with each of the cathodediffusion layer 40, opposite the PCM 25, and the gas-permeableliquid-impermeable membrane 35. The cathode capillary material 66 ispreferably a woven hydrophilic fabric or plurality of hydrophilicthreads which allow oxygen access to the cathode of the fuel cellsystem, though nonwoven materials or substrates are specifically withinthe scope of the invention. The cathode capillary material 66,preferably fabricated from of a hydrophilic material, can be connectedto the hydrophilic element 63 by the first conduit 69. Alternatively thefirst conduit 69 can be a hollow tube.

[0055] A second conduit 62 is connected to the outlet of the pump 67 anda collection reservoir 65. The second conduit 62 may be fabricated froma gas-permeable liquid-impermeable material to remove any residualgasses from the water. In addition, a check valve 62A may be placedbetween the pump 67 and the collection reservoir 65 in order to preventthe backflow of collected water into the cathode aspect of the fuelcells 60, 60A, and 60B, the saturation of hydrophilic element 63, or thefirst conduit 69. The collection reservoir 65 is preferably connected tothe fuel source, wherein the pump effluent is recirculated to adjust thefuel concentration. Alternately, the second conduit 62 may be connectedto remove the collected water to the outside environment. Power can besupplied to the pump 67 through electrical leads (not shown) from anoutside source or from the electricity produced by the fuel cell.Additional fuel cells 60A and 60B are connected to pump 67 by thirdconduits 69A and 69B, respectively, thus providing a simple system bywhich water may be removed from the cathode aspect of each fuel cell ofthe stack. Alternately, additional fuel cells 60A and 60B may beconnected to pump 67 through a connection to the first conduit 69,hydrophilic element 63 or cathode capillary material 66.

[0056] A hydrophilic material is typically used as a conduit for waterpassing from the membrane to the pump, though the use of a hollow tubeis specifically within the scope of the invention. The hydrophilicmaterial can be any hydrophilic material including a hydrophilic wick,fabric, foam, cotton thread, treated fabric, various hydrophilicpolymers including but not limited to hydrophilic polyesters, andcombinations thereof As shown in FIG. 6, the hydrophilic element 63,conduits 69, 69A, and 69B, interface 61, and cathode capillary material66 include the use of such hydrophilic material. Each of thesecomponents can be fabricated from the same type of hydrophilic material,but preferably each are made from different types of hydrophilicmaterial than one another.

[0057] The water management system of the present invention is alsosuitable for use in a DMFC system equipped with an anode recirculationconfiguration. The advantages of recirculating the anode effluent backinto the anode electrode, includes conserving unused methanol fuel andcontaining the anode effluent generated by the electrochemicaloxidation/reduction processes. A DMFC system that operates in an anoderecirculation configuration includes an external fuel source and adelivery mechanism to supply the anode electrode of the fuel cell withmethanol, typically as a methanol and water solution, and an externalair source to supply the cathode electrode with air, as an oxidizingagent. The anode effluent contains by-products of the anodic oxidationof methanol, including carbon dioxide and un-reacted methanol, while thecathode effluent contains by-products of the cathodic combination ofhydrogen ions and oxygen, as well as the product of the catalyticoxidation of any methanol that has crossed through the PCM withoutcontributing to the reaction, including water vapor, liquid water andair. Gas separators incorporated in effluent return lines are used toremove gases from effluent fluids. The gas separator incorporated in ananode effluent return line effectively separates carbon dioxide from theunused methanol solution and exhausts carbon dioxide from the DMFCsystem. Similarly, the gas separator incorporated in the cathodeeffluent return line separates gasses from liquids, allowing water to bereturned to the fuel delivery mechanism.

[0058] The operating conditions may be monitored using sensors andmeasuring devices. Operating conditions, such as pressure, temperature,humidity and the like may be measured to determine whether to increaseor decrease the flow of water from the cathode chamber, under particularcircumstances.

[0059] It should be understood that the pump need not be placed directlycontiguous to the cathode chamber, but may be placed in a differentlocation that provides the proper removal of excess water. It ispossible, for example, that additional channels may be placed atdifferent locations within the fuel cell and configured to drain waterfrom the cathode chamber. In addition, it may be desirable to configuremore than one pump, for example to maintain efficient water removal asdesired. Alternatively, it may be possible to use a single pump formultiple functions within the fuel cell system.

[0060] The invention is readily adaptable to a number of pump designsdepending on the application with which the direct oxidation fuel cellpower system is being employed. For example, the pumps may be selectedfrom a number of designs known to those skilled in the art, includingbut not limited to a piezoelectrically driven pump, a mechanical pump,or an electro-osmotic pump, and may be fabricated using conventionaltechniques.

[0061] It should be understood that the present invention provides amethod and apparatus to facilitate the removal of excess water from thecathode of a direct oxidation fuel cell. The water generated as aby-product of the reactions in the fuel cell can be recirculated toadjust the fuel concentration. A 50% aqueous solution of methanol is apreferred fuel. This allows for increased efficiency of the fuelcarrying capacity of the fuel cell while recycling the water which isgenerated in the reaction. A number of embodiments of the invention havebeen described and the embodiment best suited to a particularapplication can be selected for adaptation in that application.

[0062] The foregoing description has been directed to specificembodiments of the invention. It will be apparent, however, that othervariations and other modifications may be made to the describedembodiments, with the attainment of some or all of the advantages ofsuch, therefore, it is the object of the appended claims to cover allsuch variations and modifications as come within the true spirit andscope of the invention.

What is claimed is:
 1. A system comprising: a direct oxidation fuelcell, comprising a housing surrounding an MEA, a current collectordisposed on the outside of the MEA to collect and conduct electricalcurrent to a load, and a gas-permeable liquid-impermeable membranedisposed on a cathode-side outer surface of the current collector,wherein said MEA comprises an anode aspect, a cathode aspect, and a PCMdisposed between the anode aspect and the cathode aspect; a source offuel in communication with the anode aspect; a source of oxygen incommunication with the cathode aspect, so as to produceelectricity-generating reactions, comprising anodic disassociation of afuel and water mixture to produce carbon dioxide, protons and electronsand a cathodic combination of protons, electrons and oxygen to producewater; and a pump in fluid communication with an area between the PCMand the gas-permeable liquid-impermeable membrane, connected to removeexcess water produced at the cathode aspect.
 2. The system of claim 1,wherein said MEA comprises an anode diffusion layer, a cathode diffusionlayer, and a PCM disposed between the anode and the cathode, said PCMhaving an anode catalyst layer in intimate contact with the anodediffusion layer and a cathode catalyst layer in intimate contact withthe cathode diffusion layer.
 3. The system of claim 1, wherein said pumpis in fluid communication with the fuel source and connected to pumpwater produced at the cathode side to the fuel source to adjust the fuelconcentration to the desired level.
 4. The system of claim 1, whereinsaid pump is driven by the electricity generated by the fuel cell. 5.The system of claim 1, wherein said current collector comprises a wiremesh.
 6. The system of claim 2, wherein said cathode catalyst layercomprises platinum.
 7. The system of claim 2, wherein said anodecatalyst layer comprises a platinum/ruthenium alloy or platinum.
 8. Thesystem of claim 1, wherein said MEA comprises at least one conduit incommunication with said pump.
 9. The system of claim 1, wherein said PCMcomprises a perfluorocarbon sulfonic acid ionomer.
 10. The system ofclaim 1, wherein said fuel is organic.
 11. The system of claim 10,wherein said fuel is an aqueous solution of methanol.
 12. The system ofclaim 11, wherein said fuel is a about a 50% aqueous solution ofmethanol.
 13. The system of claim 1, wherein said pump is connected tosaid MEA by a conduit.
 14. A method for managing water in a directoxidation fuel cell, comprising: providing a direct oxidation fuel cell,comprising: a housing surrounding an MEA, a current collector disposedon the outside of the MEA to collect and conduct electrical current to aload, and a gas-permeable liquid-impermeable membrane disposed on acathode-side outer surface of the current collector, wherein said MEAcomprises an anode aspect, a cathode aspect and a PCM disposed betweenthe anode aspect and the cathode aspect; providing fuel to the anodeaspect of the fuel cell; providing oxygen to the cathode aspect of thefuel cell; and removing excess water accumulation from an area betweenthe PCM and the gas-permeable liquid-impermeable membrane.
 15. Themethod of claim 14, wherein said MEA comprises an anode diffusion layer,a cathode diffusion layer, and a PCM disposed between the anode and thecathode, said PCM having an anode catalyst layer in intimate contactwith the anode diffusion layer and a cathode catalyst layer in intimatecontact with the cathode diffusion layer.
 16. The method of claim 14,wherein said excess water is removed by a pressure differential createdin the area between the PCM and the gas-permeable liquid-impermeablemembrane.
 17. The method of claim 16, wherein said pressure differentialis created by a pump.
 18. The method of claim 17, wherein said pump is apiezoelectically driven pump, a mechanical pump, or an electro-osmoticpump.
 19. The method of claim 14, further comprising recirculating atleast a portion of the removed water to adjust the fuel concentration.20. The method of claim 14, wherein said excess water is recirculated bya pump in fluid communication with the fuel source and the area betweenthe PCM and the gas-permeable liquid-impermeable membrane to adjust thefuel concentration to a desired level.
 21. The method of claim 14,wherein said gas-permeable liquid-impermeable membrane filters theoxygen provided to the cathode aspect.
 22. The method of claim 17 or 20,wherein said pump is driven by the electricity generated by the fuelcell.
 23. The method of claim 14, wherein said fuel is organic.
 24. Themethod of claim 23, wherein said fuel is an aqueous solution ofmethanol.
 25. A method of operating a direct oxidation fuel cell,comprising: providing a direct oxidation fuel cell, comprising: ahousing surrounding an MEA, a current collector disposed on the outsideof the MEA to collect and conduct electrical current to a load, and agas-permeable liquid-impermeable membrane disposed on a cathode-sideouter surface of the current collector, wherein said MEA comprises ananode aspect, a cathode aspect and a PCM disposed between the anodeaspect and the cathode aspect; providing fuel to the anode aspect of thefuel cell; providing oxygen to the cathode aspect of the fuel cell; anddrawing air to the surface of, into or through the cathode aspect of theMEA.
 26. The method of claim 25, wherein said air is drawn through theMEA by a pressure differential created in the area between the PCM andthe gas-permeable liquid-impermeable membrane.
 27. The method of claim26, wherein said pressure differential is created by a pump.
 28. Themethod of claim 27, wherein said pump is a piezoelectically driven pump,a mechanical pump, or an electro-osmotic pump.
 29. The method of claim25, wherein said gas-permeable liquid-impermeable membrane filters theoxygen provided to the cathode.
 30. The method of claim 27, wherein saidpump is driven by the electricity generated by the fuel cell.
 31. Themethod of claim 25, wherein said MEA comprises an anode diffusion layer,a cathode diffusion layer, and a PCM disposed between the anode and thecathode, said PCM having an anode catalyst layer in intimate contactwith the anode diffusion layer and a cathode catalyst layer in intimatecontact with the cathode diffusion layer.
 32. A system comprising: adirect oxidation fuel cell, comprising a housing surrounding an MEA, acurrent collector disposed on the outside of the MEA to collect andconduct electrical current to a load, and a gas-permeableliquid-impermeable membrane disposed on a cathode-side outer surface ofthe current collector, wherein said MEA comprises an anode aspect, acathode aspect, and a PCM disposed between the anode aspect and thecathode aspect; a source of fuel in communication with the anode aspect;a source of oxygen in communication with the cathode aspect, so as toproduce electricity-generating reactions, comprising anodicdisassociation of a fuel and water mixture to produce carbon dioxide,protons and electrons and a cathodic combination of protons, electronsand oxygen to produce water; and a pump in fluid communication with anarea between the PCM and the gas-permeable liquid-impermeable membrane,to remove excess water produced at the cathode aspect, wherein saidfluid communication comprises a hydrophilic material.
 33. The system ofclaim 32, wherein the hydrophilic material is a hydrophilic fabric,foam, cotton thread, or treated fabric, hydrophilic polymer, hydrophilicpolyester, or combinations thereof.
 34. The system of claim 32, whereinthe cathode aspect further comprises a cathode capillary materialdisposed between the gas-permeable liquid-impermeable membrane and acathode diffusion layer, wherein the cathode diffusion layer is adjacentthe PCM.
 35. The system of claim 34, wherein the cathode capillarymaterial is a hydrophilic material.
 36. The system of claim 35, whereinthe hydrophilic material is a hydrophilic fabric, foam, cotton thread,or treated fabric, hydrophilic polymer, hydrophilic polyester, orcombinations thereof.
 37. The system of claim 32, wherein the pump is influid communication with more than one fuel cell of a fuel cell stack.